Ketonic perylene derivative and process of preparing same



Patented Aug. 21, 1934 1,970,? 'KETONIC PERYLENE DERIVATIVE AND PROCESS OF PREPARING SAME Cecil Shaw andRobert'Fraser Thomson, Grange-Q H mouth, Scotland, assignors to Imperial Chemical Industries Limited, a corporation of Great Britain 1 No Drawing. Application April 11, 1932, Serial H "No. 604,655. In Great Britain April 16, 1931 1 i 'i e Q -.zi0 i This. invention relates 'to the manufacture, production and use of intermediates and dye stuffs offthe anthraquinone series, and in'particular consists in new or improved processes for the manufacture and use of intermediates and dyestufisirom hydroxy or substituted hydroxy ketonic perylenes, 1 I

i It is already known that black and grey ,vat dyestufisca'n be obtained by heating certain substituted derivatives of dibenzanthrone and isodibenzanthrone containing nitrogen in the presence of solvents or diluents.

'ccording to the present invention a hydroxy or substituted hydroxyketonic peryleneis heated above about 2'10? C. with a carboxylic acid anhy- I', particular We] have found that Bz2,Bz2 di-' hydroxyor. Bz2,Bz2f -dialkoxy-dibenzanthrones, 7 when heated with aichlorinated phthali'c an ye dride at atemperature above about 300 9,, give new products which have the propertiesiof vat dyes'tufis. A surprising featureisthefact that a product can be obtained from Bz2,Bz2 ".-dihydroxydibenzanthrone, which 'isfast to acids and alkalis. We find chlorinated phthalic anhydrides are very suitable solvents, and that a very convenient temperature range is 300-400" C. The chlorinated phthalic anhydrides have the advantages'oi being stableat high temperatures, of being good solvents at these teinperatures, having low vapour pressure and consequently small fire risk, of being readily removedby extraction with v ater,and of being easily, recoverable for. reuse'; Further, in the'extrac'tion process, if the dyestufi' is'sufficientlypurefit is generally, also obtained in a very ,fineflstate of division, so that it is suitable forimmediateuse. I The. mixture of dyestuff ,and anhydride] may beheated'in the presence of small quantities of 40 metallic substances-or fsalts' and this has the effect. in certain casesof producing differencesin shadefof the resulting products, 'I n Thefollowing' examples, in which the partsare by weight, illustratebut do not limit the invention. h

Example 1 500 parts: of ph'thali'cf'anhydridev are heated to 170 C. and at this temperature 100 parts of Bz2,Bz2-dimethoxy-dibenzanthrone are gradually added. The temperature is then raised, with good stirring, until the mixture boils, and boiling is continued for about 12 hours. The mixture is then allowed to cool partially, poured out, al-

lowed to solidify, ground and treated with boiling water. [A serrate-green paste remains, which dyes cotton in Y fast shades of blue-green from a blue alkaline sodium hydrosulphite vat.

1500 parts of 3,14-diehlor o-phtha1icanhydride are melted and 100 parts of Bz2',Bz2' dimethoxydibenzanthrone added aslin Example '1." The temperature is raised to the; boiLwhich is considerablyhigher than in Example Land the mixture boiled for 2 hours. The product'is worked up asbefore. It dyes fast blue shades from a blue alkalinehydrosulphite yat. a

I H Thisis similarto'the preceding examples except that the starting material is Bz2,Bz2"-dihydroxy-dibenzanthrone 60 parts of this being heated with 320;.parts oi tetra-chloro-phthalic anhydride at about 320 0. for 12 hours. The product is a black paste, dyeing cotton in bluegrey shades of good-iastness from a blue alkaline hydrosulphite vat.

Example 4 This is similar-to Example -1, but 5 parts of copperare added tothe, melt and a green-blue product obtained.

Example 5 10 parts of the product from Example 3, in the form'of a dry, finely divided powder, are gradually added, with good stirring to a' mixture of 50 parts of molten phthalicanhydride. The temperature is thenadiusted to 180 C, and a current of chlorine gas is 'passedthrough for several hours, until a sample portionconta'ins about'35%'of chlorine. The mixture is then allowed to cool partially, poured out, allowed to' solidify, ground and thoroughly extracted with boiling water. The residue, 9 on drying, gives a black powder, dyeing cotton in greysha'des froma'green-blue alkaline hydrosulphit t- I V "Ea'amplefi I 'parts of tetrachloro. phthalicanhydride are 100 melted, and 30 parts of oxidized isodibenzanthrone gradually added, and stirred in, until a thorough mixture has been obtained. The temperatureis then raised, as quickly as possible, to 350, kept at 350 C. for a few minutes, and then the mixture cooled. After cooling partially, it is poured out, allowed to solidify, ground and extracted with hot, very dilute caustic soda solution, until all the chlorophthalic acid has been removed. The residue is then washed with water, until free from solved in 625 parts of 96% sulphuric acid, containing 12.5 parts of boric acid. This solution is cooled to 5 C., and there is then added, over a 5? period of 4 hours, 25 parts of manganese dioxide in 35 parts of 90% sulphuricacid, also at '5" C; Q

When this has been added, the temperature is adjusted to 10 C., and maintained at this'for 8' The mixture is thendilute'd'with 5000 53 parts of'sodium bisulphite are hours. parts of water. added, the whole heated to boiling for half an hour, then filtered, washedfiand dried;

. sisting: of dihydroxy-dibenzanthrone, its ethers,

, esters, and their respective halogen deriva- 30 parts of brominated Bz2,Bz2-dirnethoxy Example 7" dibenzanthrone are submitted-to a he atingtreat-. mentwith 100 parts of tetrachloro phthalic, anhydride under similar conditions to thosedescribed in Example 6. The pro'duct is also isolated in a similar manner, and'the'nforms a black powder, dissolving in concentrated sulphuricacid with a violet colour, and dyeing cotton inblue'shades from a blue alkalinehydrosulphite vat. I The brominated 12,12-dirnethoxy dibenzanthrone is prepared as follows:

56 parts of bromine are mixed with 200'parts of 100% sulphuric acid, and 20 parts of Bz2,Bz2'- dimethoxy-dibenzanthrone are then stirred in; the temperature is raised to 30-35 0., and kept at this for 18 hours with rapid stirring after which the melt isdrowned in cold water, and the dyestufi filtered off. i p Y m flm I '35 parts of tetrachloro phthalic'anhydride are melted and 10 parts of Bz2,Bz2f-diacetoxy-dibenzanthrone are then gradually stirred in; Stirring is continued until thorough mixing has been obtained, when the temperature is raised} as quickly as possible, to 350? C., maintained at this for 25 minutes, -and the mixture then cooled. Isolation is carried out as in previous examples. On drying, the product is obtained as a-bla'ck-powder, dissolving in concentrated sulphuric acid, with a violet solution, and dyeing cotton in navy blue shades from an alkaline hydrosulphite vat.

It will be understoodthatmany-variations and modifications are possible in ourpreferred procedure, without departingfrom the spirit of. this invention. 7 x r 1 In the claims below it should be understood that where new products, dyestuifs ,,o'r articlesofmanufacture are claimed, wemean to includethese bodies not only in substance, but also in whatever state they exist when applied to material dyed, printed, or pigmented therewith.

Having now particularly described and ascertained the nature of our invention, and in what manner the same is to be performed, we declare that what we claim is:

1. A process for producing novel compounds, useful as dyestuffs or intermediates for dyestuffs, which comprises heating an oxy-ketonic-perylene derivative selected from the group consisting of dihydroxy dibenzanthrone, dihydroxy isodibenzanthrone, derivatives obtained from these by substitution in the hydroxyl group, and halogen derivatives of either, above 270 0., with a phthalic anhydride compound selected from the group consisting of phthalic anhydride and its halogen derivatives.

2. A process as in claim 1, the heating being effected in the presence of a metallic catalyst.

- 3. A process as. in claim 1, the heating being 8 efiectedinthe presence of a copper catalyst.

4. As a new article of manufacture, a dyestuff compoun d 'substantially identical with the prodnot obtained by the process defined in claim 1.

5; A process for producing novel dyestuff compounds, which comprises heating an oxy-dibenzanthrone derivative selected from the group contives; above'270" C. with a phthalic anhydride compound selected fromthegroup consisting of phthalic anhydride and its'ha1ogen derivatives.

lfit' As a new article 'of manu facture,fa dyestufl compound substantially identical with the product obtained by the process defined in claim"5,.. f

.7. -A process for. producing novel dyestuif compounds, which comprises heating fan oxy-dibe'n zanthronederivative selected fromthe group consisting of di lydroxy dibenzanthron and its 'ethers above 270 C .'with 'aphthalic anhydride 19 5 compound I selected from, the group 1 consisting of plithalic anhydride and its,chloro-derivatives.

r 3.. As a new article'of manufacture, fadyestufl compoundsubstantially identical with the'product obtained by the process defined in claim '7;

9. A process for producing novel dyestuff com; pounds, which comprises heating Bz2,B z 2' dihydroxy dibeii'zanthrone" 'in tetrachloro phthalic anhydri de .at' a temperature above, 350510., until formation of thenovel dyestufl is substantially completely j 1 IOQ'As anew article of manuiacturaadyestufl compound" substantially identical with the product obtained by the process definedin claim 9.

'11. Asfa new article of manufacture a; dyestuf! compound substantially. identical with the prodnot obtained by heating an .oxy-ketonic-perylene derivative selected from the group consisting; of oxidized dibenzanthrone, oxidized. isodiberizanthrone, derivatives obtained'from, these by substitution in, the hydroxyl. group, and'halo'gen derivativesofeither, above 270? C.', with a phthalic anhydride, compound selected from the group consisting.'offphthalic anhydride and itshalogen derivatives,- in the presence of ametallic catalyst.

- 12. As a new'article otmanufacture'adyestuff compound substantially identical with" the product obtained by heatingan oxy-ketonic-perylene derivative selected fromthe'group consisting of oxidized dibenzanthrone, oxidized "isodibenzanthrone, derivatives obtained from these by substitution in the hydroxyl group, and halogen derivatives of either, above 270 C., witha phthalic anhydride compound selected from'the group consisting of phthalic anhydride and its halogen derivatives, in the presence of a copper catalyst.

CECIL SHAW. ROBERT FRASER THOMSON. 

